U.S. patent number 8,084,653 [Application Number 11/619,592] was granted by the patent office on 2011-12-27 for method for producing fluorinated organic compounds.
This patent grant is currently assigned to Honeywell International, Inc.. Invention is credited to Cheryl L. Bortz, Rajesh K. Dubey, Barbara A. Light, Jing Ji Ma, Daniel C. Merkel, Sudip Mukhopadhyay, Steven D. Phillips, Hsueh S. Tung, Michael Van Der Puy.
United States Patent |
8,084,653 |
Tung , et al. |
December 27, 2011 |
Method for producing fluorinated organic compounds
Abstract
Disclosed are processes for the production of fluorinated
olefins, preferably adapted to commercialization of
CF.sub.3CF.dbd.CH.sub.2 (1234yf). Three steps may be used in
preferred embodiments in which a feedstock such as
CCl.sub.2.dbd.CClCH.sub.2Cl (which may be purchased or synthesized
from 1,2,3-trichloropropane) is fluorinated (preferably with HF in
gas-phase in the presence of a catalyst) to synthesize a compound
such as CF.sub.3CCl.dbd.CH.sub.2, preferably in a 80-96%
selectivity. The CF.sub.3CCl.dbd.CH.sub.2 is preferably converted
to CF.sub.3CFClCH.sub.3 (244-isomer) using a SbCl.sub.5 as the
catalyst which is then transformed selectively to 1234yf,
preferably in a gas-phase catalytic reaction using activated carbon
as the catalyst. For the first step, a mixture of Cr.sub.2O.sub.3
and FeCl.sub.3/C is preferably used as the catalyst to achieve high
selectivity to CF.sub.3CCl.dbd.CH.sub.2 (96%). In the second step,
SbCl.sub.5/C is preferably used as the selective catalyst for
transforming 1233xf to 244-isomer, CF.sub.3CFClCH.sub.3. The
intermediates are preferably isolated and purified by distillation
and used in the next step without further purification, preferably
to a purity level of greater than about 95%.
Inventors: |
Tung; Hsueh S. (Getzville,
NY), Mukhopadhyay; Sudip (Williamsville, NY), Van Der
Puy; Michael (Amherst, NY), Merkel; Daniel C. (West
Seneca, NY), Ma; Jing Ji (West Seneca, NY), Bortz; Cheryl
L. (N. Tonawanda, NY), Light; Barbara A. (Niagara Falls,
NY), Phillips; Steven D. (New York, NY), Dubey; Rajesh
K. (Williamsville, NY) |
Assignee: |
Honeywell International, Inc.
(Morristown, NJ)
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Family
ID: |
46326981 |
Appl.
No.: |
11/619,592 |
Filed: |
January 3, 2007 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20070197842 A1 |
Aug 23, 2007 |
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Related U.S. Patent Documents
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Application
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Filing Date |
Patent Number |
Issue Date |
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11118504 |
Apr 29, 2005 |
7371904 |
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11118503 |
Apr 29, 2005 |
7345209 |
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11118530 |
Apr 29, 2005 |
7189884 |
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60755485 |
Jan 3, 2006 |
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60567426 |
Apr 29, 2004 |
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60567429 |
Apr 29, 2004 |
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60567427 |
Apr 29, 2004 |
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60567425 |
Apr 29, 2004 |
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60567428 |
Apr 29, 2004 |
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Current U.S.
Class: |
570/123 |
Current CPC
Class: |
C07C
17/25 (20130101); C07C 17/206 (20130101); C07C
17/278 (20130101); C07C 21/18 (20130101); C07C
17/10 (20130101); C07C 17/26 (20130101); C07C
17/272 (20130101); C07C 17/00 (20130101); C07C
17/04 (20130101); C07C 17/21 (20130101); C07C
17/204 (20130101); C07C 17/269 (20130101); C07C
17/087 (20130101); C07C 17/20 (20130101); C07C
17/04 (20130101); C07C 19/01 (20130101); C07C
17/10 (20130101); C07C 19/01 (20130101); C07C
17/25 (20130101); C07C 21/04 (20130101); C07C
17/087 (20130101); C07C 19/10 (20130101); C07C
17/204 (20130101); C07C 19/01 (20130101); C07C
17/206 (20130101); C07C 21/18 (20130101); C07C
17/21 (20130101); C07C 19/08 (20130101); C07C
17/21 (20130101); C07C 19/10 (20130101); C07C
17/25 (20130101); C07C 21/18 (20130101); C07C
17/25 (20130101); C07C 21/073 (20130101); C07C
17/00 (20130101); C07C 21/18 (20130101); C07C
17/269 (20130101); C07C 21/18 (20130101); C07C
17/272 (20130101); C07C 21/18 (20130101); C07C
17/278 (20130101); C07C 21/18 (20130101) |
Current International
Class: |
C07C
17/00 (20060101); C07C 25/13 (20060101); C07C
23/00 (20060101); C07C 21/18 (20060101); C07C
19/08 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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522639 |
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Jan 1993 |
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EP |
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0522639 |
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Jan 1993 |
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EP |
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11140002 |
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May 1999 |
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JP |
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2000169404 |
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Jun 2000 |
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JP |
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WO 9504021 |
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Feb 1995 |
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WO |
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WO/96/01797 |
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Jan 1996 |
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WO |
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WO 98/21171 |
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May 1998 |
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WO |
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WO 01/07384 |
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Feb 2001 |
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WO |
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WO2005/042451 |
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May 2005 |
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WO |
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Other References
US. Appl. No. 12/702,135, filed Feb. 2010, Mukhopadhyay et al.
cited by examiner .
Henne, Albert L. et al; Fluorinated derivatives of propane and
propylene; vol. 68; p. 496-497; 1946; XP002448570. cited by other
.
Paleta, Oldrich et al; Synthesis of perfluoroallyl chloride and
some chlorofluoropropenes; No. 6; p. 920-924; 1986; XP009088473.
cited by other .
Maria O. Burgin et al; Unimolecular reaction kinetics of
CF2CLCF2CH3 and CF2CLCF2CD3; vol. 105, p. 1615-1621; 2001
XP002448571. cited by other .
U.S. Appl. No. 10/694,273, filed Oct. 27, 2003, Singh et al. cited
by other .
Zhuranl Organicheskoi Khimii, 28(4), 672-80, (1982). cited by other
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Free-radical additions to unsaturated systems, Journal of Chemical
Society, Section C: Organic, (3), 414-21, p. 415, 1970. cited by
other.
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Primary Examiner: Sullivan; Daniel
Assistant Examiner: Brooks; Clinton
Attorney, Agent or Firm: Bradford; Bruce
Parent Case Text
CROSS-REFERENCES TO RELATED APPLICATIONS
This application is related to and claims the priority benefit of
U.S. provisional application No. 60/755485, filed Jan. 3, 2006.
This application is also a Continuation-in-Part of U.S. patent
application Ser. No. 11/118,503, (pending) filed on Apr. 29, 2005,
which in turn claims the priority benefit of U.S. Provisional
Patent Application Nos. 60/567,427 and 60/567,425 filed Apr. 16,
2004.
This application is also a Continuation-in-Part of U.S. patent
application Ser. No. 11/118,504, (pending) filed on Apr. 29, 2005,
which in turn claims the priority benefit of U.S. Provisional
Patent Application Nos. 60/567,426 and 60/567,429 filed Apr. 16,
2004.
This application is also a Continuation-in-Part of U.S. patent
application Ser. No. 11/118,530, (pending) filed on Apr. 29, 2005,
which in turn claims the priority benefit of U.S. Provisional
Patent Application No. 60/567,428.
The disclosures of each of the above-mentioned applications are
incorporated herein by reference. Also incorporated herein by
reference are the following U.S. Applications 60/733,378;
60/733,444; 60/733383; 60/733,355 and 60/733,379 each of which was
filed on Nov. 3, 2005.
Claims
What is claimed is:
1. A method for producing fluorinated organic compounds comprising
fluorinating at least one compound of Formula (IA)
C(X).sub.2.dbd.CClC(X).sub.3 (IA) to at least one compound of
Formula (IB) C(X).sub.3CClYC(X).sub.3 and dehydrohalogenating said
at least one compound of Formula (IB) to at least one compound of
Formula (II) CF.sub.3CF.dbd.CHZ (II) where each X, Y, and Z is
independently H, F, Cl, I or Br.
2. The method of claim 1 wherein said at least one compound of
Formula (IA) comprises a compound wherein each X is independently H
or Cl, and Z is H.
3. The method of claim 1 wherein Z in said compound of Formula (II)
is H.
4. The method of claim 1 wherein said at least one compound of
Formula (IA) comprises at least one tetrachloropropene.
5. The method of claim 1 wherein said at least one compound of
Formula (IA) comprises at least one tetrachloropropene.
6. The method of claim 1 wherein said at least one compound of
Formula (IA) comprises CH.sub.2.dbd.CClCCl.sub.3.
7. The method of claim 1 wherein said at least one compound of
Formula (IA) comprises CCl.sub.2.dbd.CClCH.sub.2Cl.
8. The method of claim 1 wherein said at least one compound of
Formula (IA) comprises CHCl.dbd.CClCCl.sub.2H.
9. The method of claim 1 wherein said at least one compound of
Formula (IA) is selected from the group consisting of
CH.sub.2.dbd.CClCCl.sub.3, CCl.sub.2.dbd.CClCH.sub.2Cl,
CHCl.dbd.CClCCl.sub.2H, and combinations of these.
10. The method of claim 1 wherein said at least one compound of
Formula (IA) comprises a compound wherein the terminal saturated
carbon has three (3) F substituents.
11. The method of claim 1 wherein said at least one compound of
Formula (IA) comprises a compound Formula (IAA):
C(X).sub.2.dbd.CClCF.sub.3 (IAA) wherein X is as identified in
claim 1.
12. The method of claim 11 wherein each X in said compound of
Formula (IAA) is independently H or Cl.
13. The method of claim 1 wherein said at least one compound of
Formula (IA) comprises at least one trifluoropropene.
14. The method of claim 13 wherein said at least one
trifluoropropene comprises CH.sub.2.dbd.CClCF.sub.3
(HCFC-1233xf).
15. The method of claim 1 wherein said fluorinating step comprises
fluorinating at least said Formula (IA) compound to a compound of
Formula (IAA) C(X).sub.2.dbd.CClCF.sub.3 (IAA) and then
fluorinating said compound of Formula (IAA) to a compound of
Formula (IB) C(X).sub.3CClYC(X).sub.3 (IB) wherein X and Y are each
as identified in claim 1.
16. The method of claim 15 wherein said compound of Formula (II)
comprises at least one compound in which Z is H.
17. The method of claim 15 wherein said compound of Formula (IAA)
comprises CF.sub.3CCl.dbd.CH.sub.2 (HCFC-1233xf) and is fluorinated
under conditions effective to produce at least one
monochloro-tetrafluoro-propane in accordance with Formula (IB).
18. The method of claim 17 wherein said
monochloro-tetrafluoro-propane in accordance with Formula (IB)
comprises CF.sub.3CFClCH.sub.3 (HFC-244bb).
19. The method of claim 18 wherein said CF.sub.3CFClCH.sub.3
(HFC-244bb) is dehydrohalogenated under reaction conditions
effective to produce at least one compound in accordance with
Formula (II) wherein Z is H.
20. The method of claim 19 wherein said at least one compound in
accordance with Formula (II) comprises HFO-1234yf.
21. The method of claim 19 wherein said dehydrohalogenated step
comprises at least one gas phase catalytic reaction.
22. The method of claim 1 wherein said fluorinating step comprises
at least one gas phase catalytic reaction.
23. The method of claim 1 wherein said fluorinating step comprises
exposing the compound of Formula (IA) to one or more sets of
reaction conditions effective to produce at least one compound in
accordance with Formula (II).
24. The method of claim 1 wherein said fluorinating step comprises
reacting said at least one compound of Formula (IA) under
conditions effective to produce at least one
chlorofluoropropane.
25. The method of claim 24 wherein said at least one
chlorofluoropropane is a compound in accordance with Formula (IBB):
CF.sub.3CClFC(X).sub.3 (IBB) where each X is independently F, Cl or
H.
26. The method of claim 25 wherein at least one of said X in
Formula (IBB) is H.
27. The method of claim 26 wherein all three X in Formula (IBB) are
H.
28. The method of claim 1 wherein said Formula (IB) compound has at
least two chlorines on one terminal carbon and at least two
hydrogen atoms on the other terminal carbon.
29. The method of claim 1 wherein said at least one compound of
Formula (IB) comprises at least one propane having at least four
chlorine substituents.
30. The method of claim 29 wherein said at least one compound of
Formula (IB) comprises at least one propane having at least five
chlorine substituents.
31. The method of claim 29 wherein said at least one compound of
Formula (IB) is selected from the group consisting of
CH.sub.2ClCHClCCl.sub.3, CHCl.sub.2CCl.sub.2CH.sub.2Cl,
CHCl.sub.2CHClCHCl.sub.2, and combinations thereof.
32. The method of claim 1 wherein said at least one compound of
Formula (IB) comprises 1,1,1,2-tetrafluoro-2-chloropropane or
1-chloro-1,3,3,3-tetrafluoropropane.
33. A method for producing fluorinated organic compounds comprising
dehydrohalogenating at least one compound of Formula (IB):
C(X).sub.3CCLYC(X).sub.3 (IB) to at least one compound of Formula
(II): CF.sub.3CF.dbd.CHZ wherein each X and Y are independently H
or Cl, and Z is H, F, Cl, I or Br.
34. The method of claim 33 wherein said Formula (IB) compound has
at least two chlorines on one terminal carbon and at least two
hydrogen atoms on the other terminal carbon.
35. The method of claim 33 wherein said at least one compound of
Formula (IB) comprises at least one propane having at least four
chlorine substituents.
36. The method of claim 35 wherein said at least one compound of
Formula (IB) comprises at least one propane having at least five
chlorine substituents.
37. The method of claim 36 wherein said at least one compound of
Formula (IB) comprises CH.sub.2ClCHClCCl.sub.3.
38. The method of claim 36 wherein said at least one compound of
Formula (IB) comprises CHCl.sub.2CCl.sub.2CH.sub.2Cl.
39. The method of claim 36 wherein said at least one compound of
Formula (IB) comprises CHCl.sub.2CHClCHCl.sub.2.
40. The method of claim 36 wherein said at least one compound of
Formula (IB) comprises at least one propane selected from the group
consisting of CH.sub.2ClCHClCCl.sub.3,
CHCl.sub.2CCl.sub.2CH.sub.2Cl, CHCl.sub.2CHClCHCl.sub.2, and
combinations thereof.
41. A method for producing fluorinated organic compounds comprising
fluorinating at least one compound of Formula (IA)
C(X).sub.2.dbd.CClC(X).sub.3 (IA) to at least one compound of
Formula (IAA) C(X).sub.2.dbd.CClCF.sub.3 (IAA); fluorinating said
at least one compound of Formula (IAA) to at least one compound of
Formula (IB) C(X).sub.3CClYC(X).sub.3; and dehydrohalogenating said
at least one compound of Formula (IB) to at least one compound of
Formula (II) CF.sub.3CF.dbd.CHZ (II) where each X, Y, and Z is
independently H, F, Cl, I or Br.
Description
BACKGROUND OF INVENTION
(1) Field of Invention
This invention relates to novel methods for preparing fluorinated
organic compounds, and more particularly to methods of producing
fluorinated olefins.
(2) Description of Related Art
Hydrofluorocarbons (HFC's), in particular hydrofluoroalkenes such
tetrafluoropropenes (including 2,3,3,3-tetrafluoro-1-propene
(HFO-1234yf) and 1,3,3,3-tetrafluoro-1-propene (HFO-1234ze)) have
been disclosed to be effective refrigerants, fire extinguishants,
heat transfer media, propellants, foaming agents, blowing agents,
gaseous dielectrics, sterilant carriers, polymerization media,
particulate removal fluids, carrier fluids, buffing abrasive
agents, displacement drying agents and power cycle working fluids.
Unlike chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons
(HCFCs), both of which potentially damage the Earth's ozone layer,
HFCs do not contain chlorine and thus pose no threat to the ozone
layer.
Several methods of preparing hydrofluoroalkenes are known. For
example, U.S. Pat. No. 4,900,874 (Ihara et al) describes a method
of making fluorine containing olefins by contacting hydrogen gas
with fluorinated alcohols. Although this appears to be a relatively
high-yield process, for commercial scale production the handling of
hydrogen gas at high temperature raises difficult safety related
questions. Also, the cost of producing hydrogen gas, such as
building an on-site hydrogen plant, can be in many situations
prohibitive.
U.S. Pat. No. 2,931,840 (Marquis) describes a method of making
fluorine containing olefins by pyrolysis of methyl chloride and
tetrafluoroethylene or chlorodifluoromethane. This process is a
relatively low yield process and a very large percentage of the
organic starting material is converted in this process to unwanted
and/or unimportant byproducts.
The preparation of HFO-1234yf from trifluoroacetylacetone and
sulfur tetrafluoride has been described. See Banks, et al., Journal
of Fluorine Chemistry, Vol. 82, Iss. 2, p. 171-174 (1997). Also,
U.S. Pat. No. 5,162,594 (Krespan) discloses a process wherein
tetrafluoroethylene is reacted with another fluorinated ethylene in
the liquid phase to produce a polyfluoroolefin product.
SUMMARY
Applicants have discovered a method for producing fluorinated
organic compounds, including hydrofluoropropenes, which preferably
comprises converting at least one compound of Formula (I):
C(X).sub.mCCl(Y).sub.nC(X).sub.m (I) to at least one compound of
Formula (II) CF.sub.3CF.dbd.CHZ (II) where each X, Y and Z is
independently H, F, Cl, I or Br, and each m is independently 1, 2
or 3, and n is 0 or 1. As used herein and throughout, unless
specifically indicated otherwise, the term "converting" includes
directly converting (for example, in a single reaction or under
essentially one set of reaction conditions, an example of which is
described hereinafter) and indirectly converting (for example,
through two or more reactions or using more than a single set of
reaction conditions).
In certain preferred embodiments of the invention, the compound of
Formula (I) comprises a compound wherein n is 0, each X is
independently H or Cl, and Z is H. Such preferred embodiments
include converting at least one C3 alkene in accordance with
Formula (IA): C(X).sub.2.dbd.CClC(X).sub.3 (IA) to at least one
compound of formula (II) CF.sub.3CF.dbd.CHZ (II) where each X is
independently H or Cl. Preferably the one or more compounds of
Formula (IA) are tetrachloropropene(s), and are even more
preferably selected from the group consisting of
CH.sub.2.dbd.CClCCl.sub.3, CCl.sub.2.dbd.CClCH.sub.2Cl,
CHCl.dbd.CClCCl.sub.2H, and combinations of these.
In certain preferred embodiments of the invention the compound of
Formula (I) comprises a compound wherein n is 0 and the terminal
saturated carbon has three (3) F substituents. Such preferred
embodiments include converting at least one C3 alkene in accordance
with Formula (IAA): C(X).sub.2.dbd.CClCF.sub.3 (IAA) to at least
one compound of formula (II) CF.sub.3CF.dbd.CHZ (II) where each X
is independently H or Cl. Preferably the one or more compounds of
Formula (IAA) are trifluoropropene(s). Included in the preferred
trifluorpropene compounds of the present invention is
CH.sub.2.dbd.CClCF.sub.3 (HCFC-1223xf).
In certain preferred embodiments the compound of Formula (I)
comprises a compound wherein n is 1 and each X and Y is
independently H, F or Cl. Such embodiments include converting at
least one C3 alkane of Formula (IB): C(X).sub.3CClYC(X).sub.3 (IB)
to at least one compound of formula (II) CF.sub.3CF.dbd.CHZ (II)
where each X and Y is independently H, F or Cl. In certain
preferred embodiments, the Formula (IB) compound has at least two
haologens on one terminal carbon and at least two hydrogen atoms on
the other terminal carbon. Preferably the compounds of Formula (IB)
contain at least four halogen substituents and even more preferably
at least five halogen substituents. In certainly highly preferred
embodiments, the conversion step of the present invention comprises
converting a compound of Formula (IB) wherein Y is F and all three
X on one terminal carbon are F. Preferably the compound of Formula
(IB) is a penta-halogenated propane, preferably with at least four
fluorine substituents. Even more preferably the penta-halogenated
propane of Formula (IB) comprises a tetra-fluorinated,
mono-chlorinated propane, including chlorotetrafluoropropane
(C.sub.3H.sub.3F.sub.4Cl), including all isomers thereof, such as
1,1,1,2-tetrafluoro-2-chloropropane and
1-chloro-1,3,3,3-tetrafluoropropane (HFC-244fa). Other preferred
penta-halogenated compounds of Formula (IB) include
CH.sub.2ClCHClCCl.sub.3, CHCl.sub.2CCl.sub.2CH.sub.2Cl,
CHCl.sub.2CHClCHCl.sub.2. Of course, combinations of compounds of
Formula (I), including combinations of compounds of Formulas (IA),
(IAA) and (IB) may be used.
In certain preferred embodiments, the step of converting a compound
of Formula (I) to at least one compound of Formula (II) comprises
directly converting a compound of Formula (I). In other
embodiments, the step of converting a compound of Formula (I) to at
least one compound of Formula (II) comprises indirectly converting
a compound of Formula (I).
An example of indirect conversion embodiments includes converting a
compound of Formula (IA) to a compound of Formula (IAA), then
converting said Formula (IAA) compound to a Formula (IB) compound,
and then converting the Formula (IB) to the Formula (II) compound.
In certain more specific indirect conversion embodiments, the step
of converting a compound of Formula (I) comprises providing at
least one monchlortrifluorpropene in accordance with Formula (IAA),
preferably CF.sub.3CCl.dbd.CH.sub.2 (HFO-1233xf) and reacting said
monchlortrifluorpropene under conditions effective to produce at
least one monchlortetrafluorpropane in accordance with Formula
(IB), preferably CF.sub.3CFClCH.sub.3 (HFC-244bb), which in turn is
preferably exposed to reaction conditions effective to produce at
least one compound in accordance with Formula (II), preferably
HFO-1234yf. In preferred embodiments said exposing step comprises
conducting one or more of said reactions in a gas phase in the
presence of a catalyst, preferably a metal-based catalyst. Examples
of such preferred conversion steps are disclosed more fully
hereinafter. Of course, it is contemplated that in the broad scope
of the invention that any of the Formula (I) compounds may be
converted, directly or indirectly, to a compound of Formula (II) in
view of the teachings contained herein.
In certain preferred embodiments the converting step comprises
exposing the compound of Formula (I), and preferably Formula (1A),
(IAA) or Formula (1B), to one or more sets of reaction conditions
effective to produce at least one compound in accordance with
Formula (II). It is contemplated that in certain embodiments the
exposing step comprises reacting said one or more compound(s) of
Formula (IA) or (IAA) under conditions effective to produce
chlorofluoropropane, more preferably a propane in accordance with
Formula (IBB): CF.sub.3CClFC(X).sub.3 Formula (IBB) where each X is
independently F, Cl or H. In certain preferred embodiments, at
least one of said X in Formula (IBB) is H, and even more preferably
all three X are H.
The preferred conversion step of the present invention is
preferably carried out under conditions, including the use of one
or more reactions, effective to provide a Formula (I) conversion of
at least about 50%, more preferably at least about 75%, and even
more preferably at least about 90%. In certain preferred
embodiments the conversion is at least about 95%, and more
preferably at least about 97%. Further in certain preferred
embodiments, the step of converting the compound of Formula (I) to
produce a compound of Formula (II) is conducted under conditions
effective to provide a Formula (II) yield of at least about 75%,
more preferably at least about 85%, and more preferably at least
about 90%. In certain preferred embodiments a yield of about 95% or
greater is achieved.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
One beneficial aspect of the present invention is that it enables
the production of desirable fluroolefins, preferably C3
fluoroolefins, using relatively high conversion and high
selectivity reactions. Furthermore, the present methods in certain
preferred embodiments permit the production of the desirable
fluoroolefins, either directly or indirectly, from relatively
attractive starting materials. For example, 2-chloro,
2,3,3,3-tetrafluoropropane is a compound that may in certain
embodiments be an advantageous starting material because such
products are relatively easy to handle.
Preferably the Formula (I) compound is exposed to reaction
conditions effective to produce a reaction product containing one
or more of the desired fluorolefins, preferably one or more
compounds of Formula (II). Although it is contemplated that the
exposure step in certain embodiments may effectively be carried out
in a single reaction stage and/or under a single set of reaction
conditions, as mentioned above, it is preferred in many embodiments
that the conversion stepcomprise a series of reaction stages or
conditions. In one preferred aspect of the present invention, the
conversion step comprises: (a) reacting a compound of Formula (I)
which is not a compound of Formula (IAA), preferably a compound of
Formula (IA), in a gas and/or liquid phase reaction in the presence
of at least a first catalyst to produce at least one compound of
Formula (IAA), such as a monochloro-trifluoro-propene, preferably
HFO-1233xf; (b) reacting the at least one
monochloro-trifluoro-propene compound, in a gas and/or liquid phase
and preferably in the presence of at least a catalyst, preferably a
second catalyst which is different than the first catalyst, to
produce at least one compound of Formula (IB) and even more
preferably Formula (IBB), such as monochloro-terafluoro-propane;
and (c) reacting said compound of Formula (IB), in a gas and/or
liquid phase, to produce the desired HFO, preferably HFO-1234yf.
Each of the preferred reaction steps is described in detail below,
with the headings being used for convenience but not necessarily by
way of limitation.
I. Fluorination of the Compound of Formula I(A)
One preferred reaction step in accordance with the present
invention may be described by those reactions in which the compound
of Formula (IA) is fluorinated to produce a compound of Formula
(IAA). In certain preferred embodiments, especially embodiments in
which the compound of Formula (IA) comprises
C(X).sub.2.dbd.CClC(X).sub.3, where each X is independently H or
Cl, the present converting step comprises first reacting said
compound(s) by fluorinating said compound(s), preferably with HF in
a gas phase, to produce an HFO that is at least trifluorinated,
such as HFO-1223xf. Preferably this gas phase reaction is at least
partially catalyzed.
The preferred fluorination of the compound of Formula (IA) is
preferably carried out under conditions effective to provide a
Formula (IA) conversion of at least about 50%, more preferably at
least about 75%, and even more preferably at least about 90%. In
certain preferred embodiments the conversion is at least about 95%,
and more preferably at least about 97%. Further in certain
preferred embodiments, the conversion of the compound of Formula
(IA) comprises reacting such compound under conditions effective to
produce at least one compound of Formula (IAA), such as
monochlorotrifluoropropene (preferably CF.sub.3CCl.dbd.CH.sub.2
(HFO-1233xf)) at a selectivity of at least about 50%, more
preferably at least about 70%, more preferably at least about 80%,
and even more preferably at least about 90%, with selectivities of
about 95% or greater being achieved in certain embodiments.
In general, it is possible that the fluorination reaction step can
be carried out in the liquid phase or in the gas phase, or in a
combination of gas and liquid phases, and it is contemplated that
the reaction can be carried out batch wise, continuous, or a
combination of these.
For embodiments in which the reaction comprises a liquid phase
reaction, the reaction can be catalytic or non-catalytic.
Preferably, a catalytic process is used. Lewis acid catalyst, such
as metal-halide catalysts, including antimony halides, tin halides,
thallium halides, iron halides, and combinations of two or more of
these, are preferred in certain embodiments. Metal chlorides and
metal fluorides are particularly preferred. Examples of
particularly preferred catalysts of this type include SbCl.sub.5,
SbCl.sub.3, SbF.sub.5, SnCl.sub.4, TiCl.sub.4, FeCl.sub.3 and
combinations of two or more of these.
In preferred gas phase fluorination of Formula (I) compounds,
preferably Formula (IA) compounds, the reaction is at least
partially a catalyzed reaction, and is preferably carried out on a
continuous basis by introducing a stream containing the compound of
Formula (I), preferably Formula (IA), into one or more reaction
vessels, such as a tubular reactor. In certain preferred
embodiments, the stream containing the compound of Formula (I), and
preferably Formula (IA), is preheated to a temperature of from
about 80.degree. C. to about 400.degree. C., more preferably from
about 150.degree. C. to about 400.degree. C., and in certain
embodiments preferably about 300.degree. C., and introduced into a
reaction vessel (preferably a tube reactor), which is maintained at
the desired temperature, preferably from about 80.degree. C. to
about 700.degree. C., more preferably from about 90.degree. C. to
about 600.degree. C., even more preferably in certain embodiments
from about 400.degree. C. to about 600.degree. C., more preferably
from about 450.degree. C. to about 600.degree. C., where it is
preferably contacted with catalyst and fluorinating agent, such as
HF.
Preferably the vessel is comprised of materials which are resistant
to corrosion as Hastelloy, Inconel, Monel and/or fluoropolymers
linings.
Preferably the vessel contains catalyst, for example a fixed or
fluid catalyst bed, packed with a suitable fluorination catalyst,
with suitable means to ensure that the reaction mixture is
maintained with the desired reaction temperature range.
Thus, it is contemplated that the fluorination reaction step may be
preformed using a wide variety of process parameters and process
conditions in view of the overall teachings contained herein.
However, it is preferred in certain embodiments that this reaction
step comprise a gas phase reaction, preferably in the presence of
catalyst, and even more preferably a chromium-based catalyst (such
as Cr.sub.2O.sub.3 catalyst), an iron-based catalyst (such as
FeCl.sub.3 on carbon (designated herein as FeCl.sub.3/C for
convenience), and combinations of these. In preferred embodiments,
the catalyst is a combination of the two aforementioned catalysts,
where the reaction vessel contains in a first zone the
chromium-based catalyst and in a second zone the iron-based
catalyst. The temperature of the reaction in the chromium-based
catalyst reaction is preferably kept at a temperature of from about
200.degree. C. to about 600.degree. C. and even more preferably
from about 250.degree. C. to about 500.degree. C. The temperature
of the reaction in the iron-based catalyst reaction zone is
preferably kept at a temperature of from about 80.degree. C. to
about 300.degree. C. and even more preferably from about
100.degree. C. to about 250.degree. C.
In general it is also contemplated that a wide variety of reaction
pressures may be used for the fluorination reaction, depending
again on relevant factors such as the specific catalyst being used
and the most desired reaction product. The reaction pressure can
be, for example, superatmospheric, atmospheric or under vacuum and
in certain preferred embodiments is from about 1 to about 200 psia,
and in certain embodiments from about 1 to about 120 psia.
In certain embodiments, an inert diluent gas, such as nitrogen, may
be used in combination with the other reactor feed(s).
It is contemplated that the amount of catalyst use will vary
depending on the particular parameters present in each
embodiment.
II. Fluorination of the Compound of Formula I(AA)
The compound of Formula (IAA), preferably produced as described
above, and then is preferably subject to further fluorination
reaction(s) to produce a compound of Formula (IB), such as
HCFC-244. Preferably this gas phase reaction is at least partially
catalyzed.
The fluorination of the compound of Formula (IAA) is preferably
carried out under conditions effective to provide a Formula (IAA)
conversion of at least about 40%, more preferably at least about
50%, and even more preferably at least about 60%. Further in
certain preferred embodiments, the conversion of the compound of
Formula (IA) comprises reacting such compound under conditions
effective to produce at least one monochlorotetrafluoropropane,
preferably HCFC-244, at a selectivity of at least about 70%, more
preferably at least about 80%, and even more preferably at least
about 85%, with selectivities of about 90% or greater being
achieved in certain embodiments.
In general, it is possible that this fluorination reaction step can
be carried out in the liquid phase or in the gas phase, or in a
combination of gas and liquid phases, and it is contemplated that
the reaction can be carried out batch wise, continuous, or a
combination of these.
For embodiments in which the reaction comprises a liquid phase
reaction, the reaction can be catalytic or non-catalytic.
Preferably, a catalytic process is used. Lewis acid catalyst, such
as metal-halide catalysts, including antimony halides, tin halides,
thallium halides, iron halides, and combinations of two or more of
these, are preferred in certain embodiments. Metal chlorides and
metal fluorides are particularly preferred. Examples of
particularly preferred catalysts of this type include SbCl.sub.5,
SbCl.sub.3, SbF.sub.5, SnCl.sub.4, TiCl.sub.4, FeCl.sub.3 and
combinations of two or more of these.
In preferred gas phase fluorination of Formula (IAA) compounds, the
reaction is at least partially a catalyzed reaction, and is
preferably carried out on a continuous basis by introducing a
stream containing the compound of Formula (IAA) into one or more
reaction vessels, such as a tubular reactor. In certain preferred
embodiments, the stream containing the compound of Formula (I), and
preferably Formula (IAA), is preheated to a temperature of from
about 50.degree. C. to about 400.degree. C., and in certain
embodiments preferably about 80.degree. C. In other embodiments, it
is preferred that the stream containing the compound of Formula
(I), and preferably Formula (IAA), is preheated to a temperature of
from about 150.degree. C. to about 400.degree. C., preferably about
300.degree. C. This steam, preferably after preheating, is then
preferably introduced into a reaction vessel (preferably a tube
reactor), which is maintained at the desired temperature,
preferably from about 50.degree. C. to about 250.degree. C., more
preferably from about 50.degree. C. to about 150.degree. C., where
it is preferably contacted with catalyst and fluorinating agent,
such as HF.
Preferably the vessel is comprised of materials which are resistant
to corrosion as Hastelloy, Inconel, Monel and/or fluoropolymers
linings.
Preferably the vessel contains catalyst, for example a fixed or
fluid catalyst bed, packed with a suitable fluorination catalyst,
with suitable means to ensure that the reaction mixture is
maintained within about the desired reaction temperature range.
Thus, it is contemplated that the fluorination reaction step may be
preformed using a wide variety of process parameters and process
conditions in view of the overall teachings contained herein.
However, it is preferred in certain embodiments that this reaction
step comprise a gas phase reaction, preferably in the presence of
catalyst, and even more preferably an Sb-based catalyst, such as
catalyst which is about 50 wt % SbCl.sub.5/C. Other catalysts which
may be used include: from about 3 to about 6 wt % FeCl.sub.3/C;
SbF.sub.5/C; about 20 wt % SnCl.sub.4/C; about 23 wt %
TiCl.sub.4/C; and activated carbon. Preferably the catalyst
comprises Cl.sub.2 and HF pre-treated SbCl.sub.5/C.
In general it is also contemplated that a wide variety of reaction
pressures may be used for the fluorination reaction, depending
again on relevant factors such as the specific catalyst being used
and the most desired reaction product. The reaction pressure can
be, for example, superatmospheric, atmospheric or under vacuum and
in certain preferred embodiments is from about 1 to about 200 psia,
more preferably in certain embodiments from about 1 to about 120
psia.
In certain embodiments, an inert diluent gas, such as nitrogen, may
be used in combination with the other reactor feed(s).
It is contemplated that the amount of catalyst use will vary
depending on the particular parameters present in each
embodiment.
III. Dehydrohalogenation of Formula (IB)
One preferred reaction step in accordance with the present
invention may be described by those reactions in which the compound
of Formula (IB) is dehydrohalogenated to produce a compound of
Formula (II). In certain preferred embodiments, the stream
containing the compound of Formula (IB), and preferably Formula
(IBB) is preheated to a temperature of from about 150.degree. C. to
about 400.degree. C., preferably about 350.degree. C., and
introduced into a reaction vessel, which is maintained at about the
desired temperature, preferably from about 200.degree. C. to about
700.degree. C., more preferably from about 300.degree. C. to about
700.degree. C., more preferably from about 300.degree. C. to about
450.degree. C., and more preferably in certain embodiments from
about 350.degree. C. to about 450.degree. C.
Preferably the vessel is comprised of materials which are resistant
to corrosion as Hastelloy, Inconel, Monel and/or fluoropolymers
linings. Preferably the vessel contains catalyst, for example a
fixed or fluid catalyst bed, packed with a suitable
dehydrohalogenation catalyst, with suitable means to heat the
reaction mixture to about the desired reaction temperature.
Thus, it is contemplated that the dehydrohalogenation reaction step
may be preformed using a wide variety of process parameters and
process conditions in view of the overall teachings contained
herein. However, it is preferred in certain embodiments that this
reaction step comprise a gas phase reaction, preferably in the
presence of catalyst, and even more preferably a carbon- and/or
metal-based catalyst, preferably activated carbon, a nickel-based
catalyst (such as Ni-mesh) and combinations of these. Other
catalysts and catalyst supports may be used, including palladium on
carbon, palladium-based catalyst (including palladium on aluminum
oxides), and it is expected that many other catalysts may be used
depending on the requirements of particular embodiments in view of
the teachings contained herein. Of course, two or more any of these
catalysts, or other catalysts not named here, may be used in
combination.
The gas phase dehydrohalogenation reaction may be conducted, for
example, by introducing a gaseous form of a compound of Formula
(IB) into a suitable reaction vessel or reactor. Preferably the
vessel is comprised of materials which are resistant to corrosion
as Hastelloy, Inconel, Monel and/or fluoropolymers linings.
Preferably the vessel contains catalyst, for example a fixed or
fluid catalyst bed, packed with a suitable dehydrohalogenation
catalyst, with suitable means to heat the reaction mixture to about
the desired reaction temperature.
While it is contemplated that a wide variety of reaction
temperatures may be used, depending on relevant factors such as the
catalyst being used and the most desired reaction product, it is
generally preferred that the reaction temperature for the
dehydrohalogentation step is from about 200.degree. C. to about
800.degree. C., more preferably from about 400.degree. C. to about
800.degree. C., and even more preferably from about 400.degree. C.
to about 500.degree. C., and more preferably in certain embodiments
from about 300.degree. C. to about 500.degree. C.
In general it is also contemplated that a wide variety of reaction
pressures may be used, depending again on relevant factors such as
the specific catalyst being used and the most desired reaction
product. The reaction pressure can be, for example,
superatmospheric, atmospheric or under vacuum, and in certain
preferred embodiments is from about 1 to about 200 psia, and even
more preferably in certain embodiments from about 1 to about 120
psia.
In certain embodiments, an inert diluent gas, such as nitrogen, may
be used in combination with the other reactor feed(s). When such a
diluent is used, it is generally preferred that the compound of
Formula (I), preferably Formula (IB), comprise from about 50% to
greater than 99% by weight based on the combined weight of diluent
and Formula (I) compound.
It is contemplated that the amount of catalyst use will vary
depending on the particular parameters present in each
embodiment.
Preferably in such dehydrofluorination embodiments as described in
this section, the conversion of the Formula (IB) compound is at
least about 60%, more preferably at least about 75%, and even more
preferably at least about 90%. Preferably in such embodiments, the
selectivity to compound of Formula (II), preferably HFO-1234yf, is
at least about 50%, more preferably at least about 70% and more
preferably at least about 80%.
EXAMPLES
Additional features of the present invention are provided in the
following examples, which should not be construed as limiting the
claims in any way.
Example 1
Preparation of CH.sub.2.dbd.CClCH.sub.2Cl(2,3-Dichloro-1-propene)
from CH.sub.2ClCHClCH.sub.2Cl
About 8500 grams of 1,2,3-trichloropropane and about 88.0 grams
Aliquat 336 were charged into a 30 liter glass vessel, equipped
with TEFLON.RTM. shaft and stir blades, heated with internal
TEFLON.RTM. coated copper coils and refrigerant/heating circulation
bath and refrigerated condenser. The mixture was then heated to
about 73.degree. C. with medium speed agitation. At this
temperature, about 10,000 grams of 25 wt % NaOH/H2O solution is
added into the reactor from a separate container over a 2 hour
period of time. The pH was kept at about 14. After addition, the
reaction progress was monitored by GC and GC/MS. The conversion of
1,2,3-trichloropropane was about 97.5% and the selectivity to
CH.sub.2.dbd.CClCH.sub.2Cl was about 95.4%. After the stipulated
reaction time, the mixture was cooled and about 4.0 liters of
distilled and ionized water was added into the mixture. The mixture
was stirred for about 10 minutes and allowed to separate. The lower
layer product (boiling point of about 92.5.degree. C.) was drained
and distilled to substantially isolate and purify product. The
crude yield before distillation was about 6408 grams (GC purity of
about 93%).
Example 2
Preparation of HCCl.sub.2CCl.sub.2CH.sub.2Cl from
CH.sub.2.dbd.CClCH.sub.2Cl
Chlorine was bubbled into about 82.4 g of 2,3-dichloropropene at
about 10 to about 30.degree. C. with the aid of ice bath cooling
until a pale yellow color persisted for about 45 minutes. The crude
product in an amount of about 130.4 g, consisted of about 93.6%
CH.sub.2ClCCl.sub.2CH.sub.2Cl and about 2.6%
2,3-dichloropropene.
Five hundred grams of CH.sub.2ClCCl.sub.2CH.sub.2Cl was charged
into a photoreactor. The jacket for the reactor as well as the
jacket for the 450 W UV lamp were cooled to about 15.degree. C.
using a circulating cooling bath. A total of about 150 g of
chlorine was bubbled into the organic liquid over a period of about
2 hours. The crude product weighed about 591 g. GC analysis
indicated a conversion of about 54.4% and selectivity for the
desired HCCl.sub.2CCl.sub.2CH.sub.2Cl of about 87%. Distillation
provided HCCl.sub.2CCl.sub.2CH.sub.2Cl in 99% purity.
Example 3
Preparation of CCl.sub.2.dbd.CClCH.sub.2Cl from
HCCl.sub.2CCl.sub.2CH.sub.2Cl
Aliquat-336.RTM. (about 0.26 g) and about 24.8 g of
HCCl.sub.2CCl.sub.2CH.sub.2Cl were stirred rapidly at room
temperature while adding about 20 g of 25% aqueous NaOH over 19
minutes. Stirring was continued overnight before adding 30 mL water
and allowing the phases to separate. The lower organic phase, in an
amount of about 19.8 g, was about 97.5% pure
CCl.sub.2.dbd.CClCH.sub.2Clby GC analysis (96% yield). Prior to
fluorination, it was distilled (bp about 69 to about 72.degree. C.
at about 30 mm Hg) to remove any phase transfer catalyst. H NMR:
.delta. 4.41 (s) ppm.
Example 4
Selective Catalyzed-transformation of CCl.sub.2.dbd.CClCH.sub.2Cl
to CF.sub.3CCl.dbd.CH.sub.2 (HFO-1233xf) in Gas-Phase
An 22-inch long and 1/2-inch diameter Monel pipe gas-phase reactor
is charged with about 120 cc of a catalyst or a mixture of two
catalysts. In case of a mixture, Cr.sub.2O.sub.3 catalyst is kept
at the bottom zone of the reactor at a constant temperature of
about 270.degree. C.-500.degree. C. and the other catalyst, such as
FeCl.sub.3/C, is kept at the middle and the top zone of the reactor
at a constant temperature of about 120.degree. C.-220.degree. C.
The reactor is mounted inside a heater with three zones (top,
middle, and bottom). The reactor temperature is read by
custom-made-5-point thermocouples kept inside at the middle of the
reactor. The bottom of the reactor is connected to a pre-heater,
which is kept at 300.degree. C. by electrical heating. The
liquid-HF is fed from a cylinder into the pre-heater through a
needle valve, liquid mass-flow meter, and a research control valve
at a constant flow of about 1 to about 1000 grams pre hour (g/h).
The HF cylinder is kept at a constant pressure of 45 psig by
applying anhydrous N.sub.2 gas pressure into the cylinder head
space. About 10 to about 1000 g/h of CCl.sub.2.dbd.CClCH.sub.2Cl is
fed as a liquid through a dip tube from a cylinder under about 45
psig of N.sub.2 pressure. The organic flows from the dip tube to
the preheater (kept at about 250.degree. C.) through a needle
valve, liquid mass-flow meter, and a research control valve at a
constant flow of 1-1000 g/h. The organic is also fed as a gas while
heating the cylinder containing organic at about 220.degree. C. The
gas coming out of the cylinder is passed through a needle valve and
a mass flow controller into the preheater. The organic line from
the cylinder to the pre-heater is kept at about 200.degree. C. by
wrapping with constant temperature heat trace and electrical
heating elements. All feed cylinders are mounted on scales to
monitor their weight by difference. The catalysts are dried at the
reaction temperature over a period of about 8 hours and then
pretreated with about 50 g/h of HF under atmospheric pressure over
a period of about 6 hours and then under 50 psig HF pressure over
another period of about 6 hours before contacting with organic feed
containing CCl.sub.2.dbd.CClCH.sub.2Cl. The reactions are run at a
constant reactor pressure of about 0 to about 150 psig by
controlling the flow of reactor exit gases by another research
control valve. The gases exiting reactor are analyzed by on-line GC
and GC/MS connected through a hotbox valve arrangement to prevent
condensation. The conversion of CCl.sub.2.dbd.CClCH.sub.2Cl is
about 70 to about 100% and the selectivity to 1233xf is about 80%
to about 95%, respectively. The product is collected by flowing the
reactor exit gases through a scrubber solution comprising about 20
wt % to about 60 wt %. KOH in water and then trapping the exit
gases from the scrubber into a cylinder kept in dry ice or liquid
N.sub.2. The product, 1233xf is then substantially isolated by
distillation. The results are tabulated in Table 1.
TABLE-US-00001 TABLE 1 Transformation of
CCl.sub.2.dbd.CClCH.sub.2Cl to CF.sub.3CCl.dbd.CH.sub.2
(CCl.sub.2.dbd.CClCH.sub.2Cl + 3HF .fwdarw.
CF.sub.3CCl.dbd.CH.sub.2 + 3HCl) HF T, flow,
CCl.sub.2.dbd.CClCH.sub.2Cl % Conv of % Sel to # Catalyst .degree.
C. g/h flow, g/h CCl.sub.2.dbd.CClCH.sub.2Cl 1233xf 1 10% v/v
Cr.sub.2O.sub.3- 350/150 50 12 79 81 90% v/v FeCl.sub.3/C 2 20% v/v
Cr.sub.2O.sub.3- 350/150 50 12 83 86 80% v/v FeCl.sub.3/C 3 30% v/v
Cr.sub.2O.sub.3- 350/150 50 12 89 96 70% v/v FeCl.sub.3/C 4 30% v/v
Cr.sub.2O.sub.3- 350/150 70 12 79 93 70% v/v FeCl.sub.3/C 5 30% v/v
Cr.sub.2O.sub.3- 345/170 50 25 85 90 70% v/v FeCl.sub.3/C 6
Cr.sub.2O.sub.3 350 50 20 90 93 7 FeCl.sub.3/C 150 50 20 74 39 8
SbCl.sub.5/C 150 50 20 81 52 Reaction conditions: Catalyst used
(total) 120 cc; pressure, 1.5 psig;
Examples 5A and 5B
Liquid-phase Catalytic Fluorination of CF.sub.3CCl.dbd.CH.sub.2
(1233xf) with HF to CF.sub.3CFClCH.sub.3 (244bb)
Example 5A
About 327 grams of HF, about 50 grams 1233xf, and about 75 grams
SbCl.sub.5 were charged into a 1-L autoclave. The reaction mixture
was stirred at a temperature of about 80.degree. C. for about 3
hours under about 620 psig of pressure. After the reaction, the
reactor was cooled to about 0.degree. C. and about 300 ml water was
then added slowly into the autoclave over a period of about 45 min.
After complete addition of water under stirring, the reactor was
cooled to room temperature and then the overhead gases were
transferred to another collecting cylinder. The yield of
CF.sub.3CFClCH.sub.3 was about 90% at a 1233xf conversion level of
about 98%. The other major by-products were
CF.sub.3CF.sub.2CH.sub.3 (2%), and an unidentified isomer of a C4
compound of the general formula, C.sub.4H.sub.3Cl.sub.3F.sub.4
(8%).
Example 5B
About 327 grams HF, about 50 grams 1233xf, and about 75 grams
SbCl.sub.5 were charged into a 1-L autoclave. The reaction mixture
was stirred at 80.degree. C. for about 3 hours under about 625 psig
of pressure. After the reaction, the reactor was cooled to about
45.degree. C. and then the overhead gas mixture was passed through
a well dried KF, NaF, or Al.sub.2O.sub.3 (350 g) packed column kept
at about 80.degree. C. to strip off HF from the gas stream. The
gases coming out of the column are collected in a cylinder kept in
dry ice (-70.degree. C.) bath. The yield of CF.sub.3CFClCH.sub.3
was 87% at a 1233xf conversion level of 93%. The other major
by-products were CF.sub.3CF.sub.2CH.sub.3 (1%), and an unidentified
isomer of a C4 compound of the general formula,
C.sub.4H.sub.3Cl.sub.3F.sub.4 (7%). The product,
CF.sub.3CFClCH.sub.3 was isolated by distillation with 98%
purity.
Example 6
Gas-phase Catalytic Fluorination of CF.sub.3CCl.dbd.CH.sub.2
(1233xf) with HF to CF.sub.3CFClCH.sub.3 (244bb)
A 22-inch (1/2-inch diameter) Monel tube gas phase reactor was
charged with about 120 cc of a catalyst. The reactor was mounted
inside a heater with three zones (top, middle and bottom). The
reactor temperature was read by a custom made 5-point thermocouple
kept at the middle inside of the reactor. The inlet of the reactor
was connected to a pre-heater, which was kept at about 300.degree.
C. by electrical heating. Organic (1233xf) was fed from a cylinder
kept at 70.degree. C. through a regulator, needle valve, and a gas
mass-flow-meter. The organic line to the pre-heater was heat traced
and kept at a constant temperature of about 73.degree. C. by
electrical heating to avoid condensation. N.sub.2 was used as a
diluent in some cases and fed from a cylinder through a regulator
and a mass flow controller into the pre-heater. All feed cylinders
were mounted on scales to monitor their weight by difference. The
reactions were run at a constant reactor pressure of from about 0
to about 100 psig by controlling the flow of reactor exit gases by
another research control valve. The gas mixtures exiting reactor
was analyzed by on-line GC and GC/MS connected through a hotbox
valve arrangements to prevent condensation. The conversion of
1233xf was from about 50% to about 65% and the selectivity to 244
isomer (CF.sub.3CFClCH.sub.3) was from about 90% to about 93%
depending on the reaction conditions using 120 cc of 50 wt %
SbCl.sub.5/C as the catalyst at about 65.degree. C. to about
-85.degree. C. with a HF flow of about 50 g/h and organic flow of
about 15 g/h. No CF.sub.3CF.sub.2CH.sub.3 was observed under the
reaction conditions. The catalyst is pretreated at first with 50
g/h HF at about 65.degree. C. for about 2 hours and then with about
50 g/h HF and about 200 sccm of Cl.sub.2 at about 65.degree. C. for
about 4 hours. After pre-treatment, about 50 sccm of N.sub.2 is
flows over a period of about 40 minutes through the catalyst bed to
sweep free chlorine from the catalyst surface prior to interacting
with the organic feed (1233xf). Pretreatment is considered
important to many embodiments of the invention. The products were
collected by flowing the reactor exit gases through a 20-60 wt %
aqueous KOH scrubber solution and then trapping the exit gases from
the scrubber into a cylinder kept in dry ice or liquid N.sub.2. The
products were then isolated by distillation. About 50 wt %
SbCl.sub.5/C, about 3 to about 6 wt % FeCl.sub.3/C, 20 wt %
SnCl.sub.4/C, and about 23 wt % TiCl.sub.4/C, using 4 different
kind of activated carbon such as Shiro saga, Calgon, Norit, and
Aldrich were used as the catalyst at from about 60 to about
150.degree. C. Among all the catalysts used for this reaction,
Cl.sub.2 and HF pre-treated SbCl.sub.5/C was found to be generally
preferred in terms of activity. The results using SbCl.sub.5 as the
catalyst are shown in Table 2.
TABLE-US-00002 TABLE 2 Catalyzed-gas-phase transformation of
CF.sub.3CCl.dbd.CH.sub.2 to CF.sub.3CFClCH.sub.3 Conv. of T,
CF.sub.3CCl.dbd.CH.sub.2 Sel. to # Cat .degree. C. (1233xf)
CF.sub.3CFClCH.sub.3 1 10 wt % SbCl.sub.5/C 60 15 100 2 20 wt %
SbCl.sub.5/C 60 21 98 3 30 wt % SbCl.sub.5/C 60 32 98 4 50 wt %
SbCl.sub.5/C 60 55 97 5 50 wt % SbCl.sub.5/C 80 62 93 6 50 wt %
SbCl.sub.5/C 100 56 87 7 60 wt % SbCl.sub.5/C 60 59 91 8 50 wt %
SbCl.sub.5/ 60 34 92 NORIT RFC 3 Activated Carbon 9 50 wt %
SbCl.sub.5/ 60 56 96 Shiro Saga Activated Carbon 10 50 wt %
SbCl.sub.5/ 60 57 94 Aldrich Activated Carbon Reaction conditions:
1233xf flow, 150 sccm; HF flow 50 g/h; pressure, 2.5-5.3 psig; in
1-5 reactions Calgon activated carbon is used as the catalyst
support; catalyst, 120 cc. All catalysts are pre-treated with
Cl.sub.2 and HF prior to contacting with 1233xf.
Example 7
Conversion of CF.sub.3CFClCH.sub.3 to CF.sub.3CF.dbd.CH.sub.2 in
Gas-phase
A 22-inch (1/2-inch diameter) Monel tube gas phase reactor was
charged with 120 cc of catalyst. The reactor was mounted inside a
heater with three zones (top, middle and bottom). The reactor
temperature was read by custom made 5-point thermocouples kept at
the middle inside of the reactor. The inlet of the reactor was
connected to a pre-heater, which was kept at about 300.degree. C.
by electrical heating. Organic (CF.sub.3CFClCH.sub.3) was fed from
a cylinder kept at about 65.degree. C. through a regulator, needle
valve, and a gas mass-flow-meter. The organic line to the
pre-heater was heat traced and kept at a constant temperature of
from about 65.degree. C. to about 70.degree. C. by electrical
heating to avoid condensation. The feed cylinder was mounted on
scales to monitor their weight by difference. The reactions were
run at a constant reactor pressure of from about 0 to about 100
psig by controlling the flow of reactor exit gases by another
research control valve. The gas mixture exiting reactor was
analyzed by on-line GC and GC/MS connected through a hotbox valve
arrangement to prevent condensation. The conversion of
CF.sub.3CFClCH.sub.3 was almost 98% and the selectivity to
HFO-1234yf was from about 69% to about 86% depending on the
reaction conditions. The products were collected by flowing the
reactor exit gases through a about 20 wt % to about 60 wt % of
aquesous KOH scrubber solution and then trapping the exit gases
from the scrubber into a cylinder kept in dry ice or liquid
N.sub.2. The products were then isolated by distillation. Results
are tabulated in Table 3.
TABLE-US-00003 TABLE 3 Catalyzed-transformation of
CF.sub.3CFClCH.sub.3 to HFO-1234yf Flow rate, CF.sub.3CFClCH.sub.3
Conversion 1234yf # Cat T, .degree. C. (244 isomer) sccm of 244
(Sel. %) 1 A 400 150 100 46 2 B 400 150 96 63 3 C 400 100 100 64 4
D 400 100 99 93 5 D 400 150 92 89 6 E 400 100 96 56 7 F 400 100 87
51 8 G 400 100 100 37 Reaction conditions: pressure, 2.5-5.3 psig;
catalyst, 100 cc, A is NORIT RFC 3; B is Shiro-Saga activated
carbon; C is Aldrich activated carbon; D is Calgon activated
carbon; activated carbon; E is 0.5 wt % Pd/C; F is 0.5 wt % Pt/C; G
is Ni-mesh; Organic cylinder temperature-65.degree. C.;
CF.sub.3CFClCH.sub.3 (244) line to the preheater-60.degree. C.;
Preheater, 350.degree. C.; P-5 psig.
Example 8
Selective Catalyzed-transformation of CCl.sub.3CCl.dbd.CH.sub.2 to
CF.sub.3CCl.dbd.CH.sub.2 (HFO-1233xf) in Gas-Phase
A 22-inch long and 1/2-inch diameter Monel pipe gas phase reactor
was charged with 120 cc of a catalyst or a mixture of two
catalysts. In case of a mixture, Cr.sub.2O.sub.3 catalyst is kept
at the bottom zone of the reactor at a substantially constant
temperature of from about 270.degree. C. to about 500.degree. C.
and the other catalyst, such as FeCl.sub.3/C is kept at the middle
and the top zone of the reactor at a substantially constant
temperature of from about 120.degree. C. to about 220.degree. C.
The reactor was mounted inside a heater with three zones (top,
middle, and bottom). The reactor temperature was read by
custom-made-5-point thermocouples kept inside at the middle of the
reactor. The bottom of the reactor was connected to a pre-heater,
which was kept at about 300.degree. C. by electrical heating. The
liquid-HF was fed from a cylinder into the pre-heater through a
needle valve, liquid mass-flow meter, and a research control valve
at a substantially constant flow of from about 1 to about 1000 g/h.
The HF cylinder was kept at a substantially constant pressure of
about 45 psig by applying anhydrous N.sub.2 gas pressure into the
cylinder head space. A feed rate of from about 10 g/h to about 1000
g/h of CCl.sub.3CCl.dbd.CH.sub.2 was fed as a liquid through a dip
tube from a cylinder under about 45 psig of N.sub.2 pressure. The
organic was flown from the dip tube to the pre-heater (kept at
about 250.degree. C.) through needle valve, liquid mass-flow meter,
and a research control valve at a substantially constant flow of
from about 1 to about 1000 g/h. The organic is also fed as a gas
while heating the cylinder containing organic at about 220.degree.
C. The gas effluent from the cylinder is passed through a needle
valve and a mass flow controller into the pre-heater. The organic
line from the cylinder to the pre-heater was kept at about
200.degree. C. by wrapping with constant temperature heat trace and
electrical heating elements. All feed cylinders were mounted on
scales to monitor their weight by difference. The catalysts were
dried at the reaction temperature over a period of about 8 hours
and then pretreated with about 50 g/h of HF under atmospheric
pressure over a 6 hour period and then under about 50 psig HF
pressure over a 6 hour period before contacting with organic feed,
CCl.sub.3CCl.dbd.CH.sub.2. The reactions were run at a
substantially constant reactor pressure ranging from about 0 to
about 150 psig by controlling the flow of reactor exit gases by
another research control valve. Those gases exiting reactor were
analyzed by on-line GC and GC/MS connected through a hotbox valve
arrangements to prevent condensation. The conversion of
CCl.sub.3CCl.dbd.CH.sub.2 was in a range of from about 90% to about
100% and the selectivity to CF.sub.3CCl.dbd.CH.sub.2 (1233xf) was
about 79%. The effluent contained in addition HFO-1243zf in an
amount of about 7.7%, 1232-isomer in an amount of about 1.3%, and
1223 in an amount of about 0.8%, and an unidentified byproduct. The
product was collected by flowing the reactor exit gases through a
20-60 wt % aq. KOH scrubber solution and then trapping the exit
gases from the scrubber into a cylinder kept in dry ice or liquid
N.sub.2. The product, 1233xf was then substantially isolated by
distillation. Using only Cr.sub.2O.sub.3 catalyst, a selectivity of
about 68% to 1233xf at a conversion level of about 79% was
achieved.
Examples 9A-9D
Direct Liquid-phase Catalytic Fluorination of
CCl.sub.3CCl.dbd.CH.sub.2 with HF to CF.sub.3CFClCH.sub.3
(244-isomer)
Example 9A
About 327 grams HF, about 50 grams CCl.sub.3CCl.dbd.CH.sub.2, and
about 75 grams SbCl.sub.5 were charged into a 1-L autoclave. The
reaction mixture was stirred at about 80.degree. C. for about 3
hours under about 610 psig of pressure. After the reaction, the
reactor was cooled to about 40.degree. C. and about 300 ml water
was then added slowly into the autoclave over a period of about 45
min. After complete addition of water under stirring, the reactor
was cooled to about room temperature and then the overhead gases
were transferred to another collecting cylinder. The yield of
CF.sub.3CFClCH.sub.3 was about 89% at a CCl.sub.3CCl.dbd.CH.sub.2
conversion level of about 88%. The other major by-products were
CF.sub.3CF.sub.2CH.sub.3 (2%), and an unidentified isomer of a C4
compound of the general formula, C.sub.4H.sub.3Cl.sub.3F.sub.4
(8%).
Example 9B
About 327 grams HF, about 50 grams CCl.sub.3CCl.dbd.CH.sub.2, and
about 75 grams SbCl.sub.5 were charged into a 1-L autoclave. The
reaction mixture was stirred at about 100.degree. C. for about 3
hours under about 685 psig of pressure. After the reaction, the
reactor was cooled to about 40.degree. C. and about 300 ml water
was then added slowly into the autoclave over a period of about 45
minutes. After complete addition of water under stirring, the
reactor was cooled to room temperature and then the overhead gases
were transferred to another collecting cylinder. The yield of
CF.sub.3CFClCH.sub.3 was about 78% at a CCl.sub.3CCl.dbd.CH.sub.2
conversion level of about 100%. The other major by-products were
CF.sub.3CF.sub.2CH.sub.3 (about 4%), and an unidentified isomer of
a C4 compound of the general formula, C.sub.4H.sub.3Cl.sub.3F.sub.4
(about 13%).
Example 9C
About 327 grams HF, about 50 grams CCl.sub.3CCl.dbd.CH.sub.2, and
about 75 grams SbCl5 were charged into a 1-L autoclave. The
reaction mixture was stirred at about 125.degree. C. for about 6
hours under about 825 psig of pressure. After the reaction, the
reactor was cooled to about 40.degree. C. and about 300 ml water
was then added slowly into the autoclave over a period of about 45
min. After complete addition of water under stirring, the reactor
was cooled to about room temperature and then the overhead gases
were transferred to another collecting cylinder. The major products
were CF.sub.3CF.sub.2CH.sub.3 (about 53%) and CF.sub.3CFClCH.sub.3
(about 25%) at a CCl.sub.3CCl.dbd.CH.sub.2 conversion level of
about 100%. The other major by-products were and unidentified
isomer of a C4 compound of the general formula,
C.sub.4H.sub.3Cl.sub.3F.sub.4 (8%) and tar.
Example 9D
About 327 grams HF, about 50 grams CCl.sub.3CCl.dbd.CH.sub.2, and
about 75 g SbCl.sub.5 were charged into a 1-L autoclave. The
reaction mixture was stirred at about 150.degree. C. for about 6
hours under about 825 psig of pressure. After the reaction, the
reactor was cooled to about 40.degree. C. and about 300 ml water
was then added slowly into the autoclave over a period of about 45
minutes. After complete addition of water under stirring, the
reactor was cooled to about room temperature and then the overhead
gases were transferred to another collecting cylinder. The major
products were CF.sub.3CF.sub.2CH.sub.3 (about 57%) and
CF.sub.3CFClCH.sub.3 (about 15%) at a CCl.sub.3CCl.dbd.CH.sub.2
conversion level of about 100%. The other major by-products were
and unidentified isomer of a C4 compound of the general formula,
C.sub.4H.sub.3Cl.sub.3F.sub.4 (about 11%) and tar.
Example 10
Catalytic Conversion of CF.sub.3CF.sub.2CH.sub.3 to
CF.sub.3CF.dbd.CH.sub.2
A 22-inch (1/2-inch diameter) Monel tube gas phase reactor was
charged with 120 cc of a catalyst. The reactor was mounted inside a
heater with three zones (top, middle and bottom). The reactor
temperature was read by custom made 5-point thermocouples kept at
the middle inside of the reactor. The inlet of the reactor was
connected to a pre-heater, which was kept at about 300.degree. C.
by electrical heating. Organic material (245 cb) was fed from a
cylinder kept at about 65.degree. C. through a regulator, needle
valve, and a gas mass-flow-meter. The organic line to the
pre-heater was heat traced and kept at a substantially constant
temperature in a range of from about 65.degree. C. to about
70.degree. C. by electrical heating to avoid condensation. The feed
cylinder was mounted on a scale to monitor its weight by
difference. The reactions were run at a substantially constant
reactor pressure of from about 0 to about 100 psig by controlling
the flow of reactor exit gases by another research control valve.
The gas mixtures exiting reactor was analyzed by on-line GC and
GC/MS connected through a hotbox valve arrangements to prevent
condensation. The conversion of 245 cb was in the range of from
about 30% to about 70% and the selectivity to 1234yf was in the
range of from about 90% 5 o about 100% depending on the reaction
conditions. The products were collected by flowing the reactor exit
gases through a 20-60-wt % of aq. KOH scrubber solution and then
trapping the exit gases from the scrubber into a cylinder kept in
dry ice or liquid N.sub.2. The products were then substantially
isolated by distillation. Results are tabulated in Table 4.
TABLE-US-00004 TABLE 4 Transformation of CF.sub.3CF.sub.2CH.sub.3
to 1234yf T, H.sub.2, CF.sub.3CF.sub.2CH.sub.3 Conversion of 1234yf
# Cat .degree. C. sccm (245cb) sccm 245cb, % (Sel. %) 1 A 575 0 65
79 63 2 B 575 0 68 82 57 3 C 575 0 73 73 61 4 D 575 0 68 84 59 5 D
575 20 68 89 73 6 E 550 0 69 92 53 7 F 550 0 67 93 33 8 G 550 0 69
73 46 Reaction conditions: pressure, 2.5-5.3 psig; catalyst, 100
cc, A is NORIT RFC 3; B is Shiro-Saga activated carbon; C is
Aldrich activated carbon; D is Calgon activated carbon; E is 0.5 wt
% Pd/C; F is 0.5 wt % Pt/C; G is Ni-mesh; Organic cylinder
temperature is about 65.degree. C.; CF.sub.3CF.sub.2CH.sub.3 (245
cb) line to the preheater is maintained at about 50.degree. C.;
preheater temperature is maintained at about 350.degree. C.;
N.sub.2 flow is not used; pressure is maintained at about 3
psig.
Having thus described a few particular embodiments of the
invention, various alterations, modifications, and improvements
will readily occur to those skilled in the art. Such alterations,
modifications, and improvements, as are made obvious by this
disclosure, are intended to be part of this description though not
expressly stated herein, and are intended to be within the spirit
and scope of the invention. Accordingly, the foregoing description
is by way of example only, and not limiting.
* * * * *